EP0367050B1 - Procédé pour la préparation de chlorures d'acides carboxyliques - Google Patents

Procédé pour la préparation de chlorures d'acides carboxyliques Download PDF

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Publication number
EP0367050B1
EP0367050B1 EP89119548A EP89119548A EP0367050B1 EP 0367050 B1 EP0367050 B1 EP 0367050B1 EP 89119548 A EP89119548 A EP 89119548A EP 89119548 A EP89119548 A EP 89119548A EP 0367050 B1 EP0367050 B1 EP 0367050B1
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EP
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Prior art keywords
phosgene
catalyst
mol
acid chloride
reaction
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EP89119548A
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German (de)
English (en)
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EP0367050A1 (fr
Inventor
Andreas Dr. Hohmann
Enrique Dr. Freudenberg
Wolfgang Dr. Reuther
Kurt Dr. Mayer
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part

Definitions

  • Carboxylic acid chlorides can be easily prepared by reacting the corresponding carboxylic acids with phosgene. The reaction requires catalysis.
  • catalysts are Carboxamides, preferably N-alkylformamides for use (DE-A-34 39 937).
  • the range of the alkyl size for the N, N-dialkylformamides ranges from dimethylformamide to formamides with 30 C atoms (EP-A-0 050 779, DE-A-29 50 155, DE-A-19 31 074).
  • the choice of the catalyst system has a decisive influence on the course of the phosgenation of a carboxylic acid to the carboxylic acid chloride and the work-up of the batch.
  • the catalyst-containing product could also be worked up by distillation in some cases.
  • the distillation of the acid chlorides formed is not only an energy and time consuming process, but also has a number of other disadvantages.
  • DE-A-29 50 155 uses diisobutylformamide as the catalyst, which is soluble in the reaction mixture in every phase of the reaction. If a final distillation of the acid chloride is to be dispensed with, must For reasons of product purity, the proportion of soluble catalyst must be kept to a minimum. With this catalyst system, too, the catalyst cannot be reused because it is discharged with the product.
  • DE-A-22 40 883 describes the production of carboxylic acid chlorides with equimolar amounts of carboxylic acid and catalyst. To separate and recover the large amount of catalyst, however, the final addition of 3 to 4 times the reaction volume of benzene with subsequent distillation of the benzene product solution is necessary.
  • JP-10 613/68 also describes the use of large amounts of catalyst in the production of linoleic acid chloride with 10 to 50 mol% of dimethylformamide, but also 1 to 10 equivalents of dimethylformamide, based on linoleic acid used.
  • the resulting acid chloride must be distilled and partly cleaned by treatment with activated carbon. The reuse of the large amounts of catalyst is not intended.
  • phosgene-containing carboxylic acid chloride can be freed of phosgene by stripping with nitrogen for several hours and / or by applying a slight vacuum. This process is time-consuming and considerably deteriorates the space-time yield of the process.
  • the invention was based on the object of finding a process for the preparation of carboxylic acid chlorides which remedies the abovementioned disadvantages.
  • the carboxylic acid chlorides can be obtained using the following method: Liquid or gaseous phosgene is added to the reaction mixture, consisting of a carboxylic acid II and the adduct of phosgene and N, N-dialkylformamide of the formula IV.
  • the time required for gassing the phosgene can be limited to 3 to 4 hours, the phosgene being used practically quantitatively. Then allowed to sit for 1 to 2 hours and the phases are separated.
  • This reaction uses 5 to 200 mol%, preferably 10 to 100 mol%, particularly preferably 10 to 30 mol% of the adduct of phosgene and N, N-dialkylformamide IV, preferably a 1: 1 adduct, optionally in excess N, N-dialkylformamide, based on the carboxylic acid II.
  • the amount of phosgene III is essentially equimolar to the carboxylic acid II.
  • the phosgene can be mixed with inert gases.
  • the reaction can be carried out either under normal pressure or under reduced or elevated pressure.
  • the reaction temperature can be between 0 and 200 ° C. The range from 30 to 100 ° C. is preferred, a temperature from 60 to 80 ° C. being particularly preferred.
  • solvents can also be added to the reaction mixture. These must be inert under the reaction conditions, e.g. saturated aliphatic hydrocarbons, ether, acetonitrile, toluene, benzene or cyclohexane.
  • the lower phase formed by the catalyst is separated from the upper product phase.
  • the catalyst is drained into a storage vessel until it is used again.
  • the carboxylic acid chloride i.e. the upper phase to be lifted off the catalyst via a riser pipe and left in the reactor until the next reaction.
  • the carboxylic acid chloride is obtained quantitatively and in high purity. Without further cleaning, e.g. Distillation or filtration can be used.
  • a particular advantage of the process according to the invention is that the carboxylic acid chloride is free of phosgene at the end of the reaction. This means that all measures for dephosgenating the crude acid chloride can be omitted.
  • the completely unproblematic recovery and reuse of the catalyst is also particularly advantageous in the process according to the invention.
  • the process according to the invention for the production of acid chlorides from aliphatic carboxylic acids is particularly suitable for monocarboxylic acids, ie for the production of compounds having the general formula RCOX, where R represents an aliphatic hydrocarbon group and X represents chlorine.
  • the aliphatic group can be straight-chain or branched, saturated, olefinically or acetylenically unsaturated.
  • Aliphatic carboxylic acids having 8 to 30, in particular 12 to 22, carbon atoms are particularly preferred.
  • Suitable N, N-dialkylformamides are dimethyl-, ethyl-methyl-, methyl-n-propyl-, methyl-iso-propyl-, diethyl-, ethyl-n-propyl-, ethyl-isopropyl-, di-n-propyl- , n-Propyl-iso-propyl- and di-iso-propyl-formamide, dimethyl- and diethylformamide are preferred, diethylformamide is particularly preferred.
  • the lower catalyst phase (342 g activated DEF) is separated from the two-phase reaction mixture.
  • the iodine color number (IFZ) of the acid chloride is 10. Both the acid chloride and the catalyst are phosgene-free.
  • example 1 is reproduced several times.
  • the catalyst phase of the previous experiment is used as the catalyst.
  • Example 2 According to the test procedure described in Example 1, 2746 g (10 mol) of technical stearic acid and the catalyst phase obtained in Example 1 (342 g) are introduced. Then 1089 g (11 mol) of phosgene are gasified. The product phase contains 2930 g (99.9% yield) stearic acid chloride, purity 97% IR); IFZ: 30.
  • Examples 3 to 10 are carried out analogously to example 2 All acid chlorides and catalysts are phosgene-free.
  • the conversion of the stearic acid is complete.
  • the reaction batch is free of phosgene. Even after the batch has cooled to 20 ° C., the catalyst remains dissolved in the crude acid chloride.
  • the discharge of stearic acid and the catalyst contained therein is 624 g (maximum possible yield of stearic acid chloride: 579 g).
  • the unit degree of acid chloride is 84% (IR).
  • the product is brown in color (IFZ: 110).
  • the mixture is then stirred for a further 1.0 hours at 77 ° C., the stirrer is switched off and the reaction mixture is cooled to 42 ° C.
  • the lower catalyst phase 208 g activated DEF
  • the upper phase contains 2122 g of behenic acid chloride (99.2% yield, based on technical behenic acid used) with a purity of 94% (IR).
  • the iodine color number of the acid chloride is 20. Both the acid chloride and the catalyst are phosgene-free.
  • the mixture is then stirred for a further 1.0 hours at 72 ° C., the stirrer is switched off and the reaction mixture is cooled to 20 ° C.
  • the lower catalyst phase (141 g of activated DEF) is separated off from the two-phase reaction mixture after 1.5 hours.
  • the upper phase contains 1188 g tall oil fatty acid chloride (99.5% yield, based on tall oil fatty acid used) with a purity of 92% (IR).
  • IR 92%
  • the iodine color number of the acid chloride is 100. Both the acid chloride and the catalyst are phosgene-free.
  • the acid chloride contains phosgene and is dephosgenated with dry nitrogen at room temperature for 12 hours.
  • the catalyst separates out as a solid. After filtration, 2025 g (97.6% yield) of stearic acid chloride are obtained in 98% purity.
  • the phosgene-containing stearic acid chloride is dephosgenated for 3 hours at 60 ° C. with dry nitrogen.
  • the reaction approach remains homogeneous.
  • the discharge of crude acid chloride is 1435 g (maximum possible yield of stearic acid chloride 1448 g) with a purity of 96% (IR).
  • the IFZ of the brown product is 100.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (7)

1.- Procédé de préparation de chlorures d'acides carboxyliques de formule générale I
Figure imgb0011
 dans laquelle R est mis pour un radical allyle en C₈ à C₃₀, alcényle en C₈ à C₃₀ ou alcynyle en C₈ à C₃₀, à partir d'acides carboxyliques de formule générale II
Figure imgb0012
 dans laquelle R a les significations sus-indiquées, et de phosgène COCl₂ (III), en présence d'un catalyseur constitué par un produit d'addition de phosgène et de N,N-diallylformamide de formule générale IV
Figure imgb0013
 dans laquelle R¹ et R² représentent, indépendamment l'un de l'autre, des radicaux allyle en C₁ à C₃, le produit réactionnel I étant obtenu par séparation de phases, caractérisé en ce qu'on utilise II et III dans des quantités sensiblement équimolaires et en ce qu'on réutilise la phase contenant le produit d'addition catalyseur.
2.- Procédé selon la revendication 1, caractérisé en ce qu'on utilise, comme N,N-dialkylformanide, du N,N-diméthylformamide, du méthyléthylformamide ou du diéthylformamide.
3.- Procédé selon la revendication 1, caractérisé en ce qu'on utilise, comme N,N-dialkylformanide, du N,N-diéthylformamide.
4.- Procédé selon la revendication 1, caractérisé en ce qu'on utilise de 5 à 200% en moles du produit d'addition catalyseur.
5.- Procédé selon la revendication 1, caractérisé en ce qu'on utilise de 10 à 100% en moles du produit d'addition catalyseur.
6.- Procédé selon la revendication 1, caractérisé en ce qu'on utilise de 10 à 30% en moles du produit d'addition catalyseur.
7.- Procédé selon la revendication 1, caractérisé en ce qu'on utilise, comme produit d'addition catalyseur, un produit d'addition 1:1, éventuellement dans du N,N-diallylformamide en excès.
EP89119548A 1988-10-31 1989-10-21 Procédé pour la préparation de chlorures d'acides carboxyliques Expired - Lifetime EP0367050B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3836967 1988-10-31
DE3836967A DE3836967A1 (de) 1988-10-31 1988-10-31 Verfahren zur herstellung von carbonsaeurechloriden

Publications (2)

Publication Number Publication Date
EP0367050A1 EP0367050A1 (fr) 1990-05-09
EP0367050B1 true EP0367050B1 (fr) 1992-09-09

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EP89119548A Expired - Lifetime EP0367050B1 (fr) 1988-10-31 1989-10-21 Procédé pour la préparation de chlorures d'acides carboxyliques

Country Status (4)

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EP (1) EP0367050B1 (fr)
CA (1) CA2000442C (fr)
DE (2) DE3836967A1 (fr)
ES (1) ES2034554T3 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4012781A1 (de) * 1990-04-21 1991-10-24 Basf Ag Verfahren zur herstellung von carbonsaeurechloriden
US5200560A (en) * 1990-04-21 1993-04-06 Basf Aktiengesellschaft Preparation of carboxylic chlorides
DE4028774A1 (de) * 1990-09-11 1992-03-12 Basf Ag Verfahren zur herstellung von carbonsaeurechloriden
DE4039750A1 (de) * 1990-12-13 1992-06-17 Basf Ag Verfahren zur entfernung von phosgen aus abgasen
DE19943858A1 (de) 1999-09-13 2001-03-15 Basf Ag Verfahren zur Reinigung von Carbonsäurechloriden
DE19943844A1 (de) 1999-09-13 2001-03-15 Basf Ag Verfahren zur Herstellung von Carbonsäurechloriden

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2057956A1 (de) * 1970-11-25 1972-06-08 Basf Ag Verfahren zur Herstellung von aliphatischen Carbonsaeurechloriden
DE2950155A1 (de) * 1979-12-13 1981-07-02 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von carbonsaeurechloriden

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EP0367050A1 (fr) 1990-05-09
DE3836967A1 (de) 1990-05-03
CA2000442A1 (fr) 1990-04-30
CA2000442C (fr) 2000-09-19
DE58902250D1 (de) 1992-10-15
ES2034554T3 (es) 1993-04-01

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